The long-term objective of the proposed research is the development of effective chiral catalysts for erantioselective metal carbene transformations directed to the synthesis of biologically relevant organic compounds. Based on the proven catalytic capabilities of dirhodium(II) tetracarboxylates and tetracarboxamides for catalytic cyclopropanation, carbon- hydrogen insertion, and nitrogen-hydrogen insertion, dirhodium(II) tetracarboxamides that possess chiral nitrogen substituents will be prepared and evaluated for asymmetric induction in these carbenoid processes. Control of reactivity and selectivity can be achieved by structural modifications on the catalyst based on the electronic and steric influences of amide ligand substituents and, in intermolecular carbenoid reac- tions, by charges in the size of the diazo compound. The syntheses of the sesquiterpenes alpha- and beta-cuparenone by gamma-C-H insertion of reactant diazo carbonyl compounds using the chiral rhodium(II) catalysts will be used to evaluate asymmetric induction in cyclopentanone construction. Similar C-H insertion methodologies will be employed for the enantioselective syntheses of the isomeric pyrroilzidine alkaloids isoretronecanol and trachelanthamidine where the stereoselectivity of C-H insertion offers additional challenges in catalyst design. The enantioselective effectiveness of chiral rhodium(II) carboxamides for the synthesis of beta-lactam derivatives will be investigated with carbenoid N-H insertion reactions that have become a standard synthetic methodology for the preparation of carbapenam antibiotics and with beta-C-H insertion processes for beta-lactam construction that have recently been developed as a general synthetic carbenoid methodology. Investigations of intermolecular cyclopropanation reactions catalyzed by chiral rhodium(II) carboxamides will be directed to highly stereoselective, enantioselective cyclopropane syntheses.